海底甲烷缺氧氧化与冷泉碳酸盐岩沉淀动力学研究进展

海底缺氧带甲烷氧化作用是一个重要的甲烷生物地球化学过程,已被许多地球化学现象所证实。甲烷缺氧氧化有效地减少了渗漏到海水和大气中的甲烷通量,但目前仅有的数据还不能很好地限定甲烷缺氧氧化在全球甲烷循环和全球碳循环中的作用。甲烷缺氧氧化的机理还存在争议,很可能是一个"反甲烷生成"过程。在许多天然气渗漏发育区域,由于甲烷缺氧氧化作用引起环境碱度的增加而沉淀冷泉碳酸盐岩,在海底表层沉积物中形成块状碳酸盐岩结壳。但冷泉碳酸盐岩生成所需的物理化学和生物地球化学条件在很大程度上还不清楚。数值计算表明,孔隙水中溶解足够量的甲烷、冷泉渗漏强度适中、较小的生物扰动作用有利于冷泉碳酸盐岩的生成,而过高的沉积速率则抑制冷泉碳酸盐岩结壳的生成。因此,海底发育冷泉碳酸盐岩可以指示天然气渗漏系统的演化特征。     

海洋环境中甲烷好氧氧化过程的研究进展

海洋环境中微生物驱动的甲烷好氧氧化作用是甲烷迁移转化过程的关键环节之一,在降解甲烷方面的贡献不容忽视,能够有效降低甲烷大气通量、影响海洋碳循环。本文系统调研了国内外文献资料,认识到海洋环境中甲烷好氧氧化的赋存范围十分广泛,可赋存于超过3 000 m水深的深海环境、热液喷口等极端环境,其中海底高压、渗漏甲烷的动态运移等是甲烷好氧氧化所面临的特殊环境,在该赋存环境下,好氧甲烷氧化菌主要以I型氧化菌为主。I型与II型氧化菌对甲烷、微量金属元素等环境条件具有一定偏向性,并且在水体和沉积物两种赋存环境下氧化菌的类型也不尽相同。同时,在该赋存环境下甲烷好氧氧化强度存在时间或空间上的差异,受温度、甲烷浓度、氧浓度、微量金属元素等环境因子影响显著,但目前对压力以及甲烷渗漏运移状态对好氧氧化过程的影响规律认识不清。随着深海科研探索不断发展,甲烷氧化菌菌群多样性研究将更加丰富。此外,还需进一步针对海底高压渗漏状态下的好氧氧化过程开展精细研究工作,进一步理解海洋环境中甲烷的好氧氧化规律,这对深刻揭示甲烷迁移转化机制、科学评估甲烷生态环境效应具有重要意义。     

海洋沉积物中金属依赖型甲烷厌氧氧化作用研究进展及展望

海洋沉积物中大部分甲烷会通过甲烷厌氧氧化作用（anaerobic oxidation of methane, AOM）而被消耗。早期研究表明,AOM可与硫酸盐、硝酸盐和亚硝酸盐的还原作用相耦合,从而有效减少甲烷向大气的排放。最近,金属依赖型AOM（metal-AOM,活性金属氧化物还原反应驱动的AOM）被证实存在于自然界沉积物和富集培养的样品中。但是,目前仍未从自然海洋环境中分离获得能够介导metal-AOM的微生物。对海洋沉积物中metal-AOM的研究大多聚焦于热液或冷泉等海洋特殊生境,一系列研究表明地质流体在这些海底化能自养生态系统的维持和演化方面起到了重要作用,并深刻影响全球地球化学循环,因此,该科学问题研究吸引了越来越多的注意力。本文讨论了可能参与海洋沉积物中metal-AOM的微生物类群及其地球化学证据,并在前人工作基础上,以冲绳海槽冷泉-热液共生区为例,提出一种新的metal-AOM作用机制。认为在全球冷泉-热液系统相互作用地区的调查有助于更好地探讨metal-AOM的发生机制及微生物在深海生境中分布的连通性问题。     

海底甲烷冷泉特征与冷泉生态系统的群落结构

海底冷泉及冷泉生态系统是现代海洋地质学和生物学研究的前沿领域,它提升了人类对深海资源的认识和利用,拓展了深海极端环境下生命的潜在界线。综述了海底甲烷冷泉的成因、冷泉喷发的类型及其特征,海底冷泉分布、形成的主要阶段(150—100Ma BP,42—28Ma BP和12Ma BP以来)以及指示海底冷泉系统的简要特征;综述了冷泉化能自养生态系统及其食物链构成和特征,专性种、潜在专性种和非专性种的生物组成及其特征,冷泉环境中有孔虫和轻小型底栖动物的主要变化;最后划分了我国近海的冷泉区(点)并简要介绍它们的分布和特征,为开展我国近海冷泉及其冷泉生物群落的调查和研究提供了基础资料。     

海底泥火山的甲烷迁移与转化及其对海洋碳输入的影响

海底通过泥火山释放的富甲烷流体是海洋甚至大气重要的碳源之一,对该系统内甲烷迁移与转化过程开展研究,有助于精确估算其碳排放总量。系统调研了国内外文献,认识到泥火山的碳排放具有强烈的时、空变化特征。在时间上,甲烷的排放主要发生在泥火山的喷发期和平静期,而在其消亡之后只出现微量的渗漏;在空间上,一个单独的泥火山中心、翼部和外缘分别发育强甲烷气泡泄漏、中等强度富甲烷和溶解无机碳(DIC)的流体泄漏以及大面积的DIC微渗漏;甲烷厌氧氧化和碳酸盐岩沉淀作用在翼部最强,对碳排放的拦截最有效,而在中心和外缘均较慢。全球陆坡和深水盆地沉积物通过泥火山向上释放的深部来源的甲烷通量为0.02 Pg C·a-1,这些碳可能引发海水缺氧、酸化和影响海-气交换通量,从而在千年尺度甚至更短时间内影响海洋吸收大气二氧化碳的能力。将来需要进一步对海底泥火山的发育数目和喷发周期进行统计,对不同类型的泥火山开展精细调查,以准确评估沉积物中自下而上的碳排放对海洋碳循环的影响,完善全球碳循环模式。     

生物标志物及其碳同位素在冷泉区生物地球化学研究中的应用

甲烷通量在很大程度上控制着海底冷泉区生物地球化学过程及生态系统。缺氧甲烷氧化(AOM)作用是消耗CH4的一种重要途径,主要是由甲烷氧化古菌和硫酸盐还原菌共同调节的,其反应机制及碳循环可以利用生物标志物及其碳同位素比值来表征。这两种微生物所产生的特定生物标志物都具有相对负的δ13C值,且硫酸盐还原菌生物标志物的δ13C值要比古菌的略偏正,说明在AOM过程中,甲烷碳从古菌到细菌的传递。甲烷通量决定海底冷泉区微生物群落结构,通量高时以ANME-2古菌群落为主,而OH-AR和BIPH两个生物标志物指标可以指示古菌群落结构变化。所以,利用生物标志物及其δ13C值不仅能够证明AOM作用的存在和反应机制,还可以对冷泉区(尤其是古冷泉区)环境及微生物群落结构进行分析和重建。     

天然气水合物的上界面——硫酸盐还原-甲烷厌氧氧化界面

定义了海域天然气水合物成矿带的上界面。指出在地球深部存在最原始的、从根本上不依靠光合作用来生存的生命系统。根据对ODP岩心样品中微生物数量的统计,海底以下沉积层中的生物数量可能占据全球原核生物总量的70%,其生物总碳量和地球表面所有植物的碳总量相当。地球内部如此巨大的生物总量应该在地壳中的气体分布等方面起着重要作用。甲烷在地壳层中广泛存在,并主要是微生物成因的。微生物产甲烷的途径主要有两个,一是二氧化碳还原,另一个是醋酸盐发酵。相应地,参与产甲烷的微生物菌群主要是产甲烷菌和食醋酸菌。甲烷在沉积层中的厌氧氧化是一个不争的事实。该过程发生在海底以下一个非常局限的区带,称为硫酸盐还原-甲烷厌氧氧化区带。通常,这个区带很窄,仅为一个面,因此,硫酸盐还原-甲烷厌氧氧化区带又称硫酸盐还原-甲烷厌氧氧化界面。这是一个基本的生物地球化学界面,在功能上它起到屏蔽甲烷向海底和大气逸散的作用,是一个巨大的甲烷汇。甲烷的厌氧氧化同样是一个由微生物介导的过程,参与此过程的微生物主要是食甲烷古菌和硫酸盐还原菌。硫酸盐还原-甲烷厌氧氧化界面在海洋沉积层中一般深可达海底以下上百米,浅可至海底。此界面为天然气水合物的上界面,该界面以上没有甲烷水合物存在。     

南海东北部硫酸盐还原-甲烷厌氧氧化界面——海底强烈甲烷渗溢的记录

南海东北部沉积物顶空气甲烷含量较高,海底存在明显的甲烷渗溢现象。该海域6个沉积物岩心的孔隙水硫酸盐浓度和顶空气甲烷含量随深度变化而变化,出现明显的硫酸盐-甲烷互相消耗区域,硫酸盐和甲烷浓度均急剧下降。HD109、HD170、HD196A、HD200、HD319和GC10等6个岩心的硫酸盐还原-甲烷厌氧氧化界面(SMI)分别位于704、911、728、636、888、792cm处,完全落入全球水合物区富甲烷环境的SMI深度范围之内。强烈的甲烷渗溢过程使得硫酸盐-甲烷互相消耗作用加剧,并形成浅的SMI。浅的SMI显示了东北部存在强烈的甲烷渗溢活动以及强烈的甲烷厌氧氧化作用,具有天然气水合物成藏的典型特征。     

南海F站位冷泉水体中的溶解甲烷

目前对南海北部陆坡的F站位冷泉的研究多从地质和生物角度开展,而冷泉羽流在水平和垂直方向上的扩散范围尚不清晰,其影响因素尚不明确。针对该问题,于2021年6月6~23日搭乘“科学”轮对该冷泉海域的溶解甲烷进行调查,使用搭载遥控无人潜水器(Remote Operated Vehicle,ROV)和温盐深系统(Conductivity,Temperature,Depth,CTD)的采水瓶采集了该冷泉及邻近水体中从近海底(距底2.5 m)至表层(5~10 m)多个层位的水样,并使用气相色谱仪在现场分析了水样中溶解甲烷的含量。结果表明,溶解甲烷在覆盖喷口的生物繁茂区水体中的含量为6 590~11 300 nmol/L,在生物稀少的毗邻区迅速降至85.0~354.8 nmol/L。水柱剖面的测量结果显示冷泉喷口区1 000 m以深的水体中溶解甲烷含量高于背景区,而1 000 m以浅的水体中溶解甲烷的含量与背景区相同(2.01~3.90 nmol/L);自喷口区顺流向下1 500 m处,甲烷羽流信号消失。综上结果,甲烷羽流的水平扩散距离≤1 500 m,上升高度≤125 m。溶解甲烷的含量在生物繁茂区的迅速降低是由于底栖生物对溶解甲烷的摄食所致,而其在繁茂区之外扩散过程中的逐渐降低是海水湍流混合导致的稀释效应所致。     

南海北部神狐海域沉积物Fe-P-S元素地球化学特征及对甲烷渗漏的指示

神狐海域是我国天然气水合物勘探试采的重点区域,在甲烷渗漏过程中会形成黄铁矿和蓝铁矿等具有指示意义的矿物,这些矿物和Fe、P、S等元素密切相关,通过Fe-P-S等元素地球化学特征来研究该区域的甲烷渗漏对进一步了解南海水合物的成藏状况有重要意义.本研究选取南海北部神狐海域Site 2A柱状沉积物为研究对象,通过对其主微量元...     

The influence of coupling mode of methane leakage and debris input on anaerobic oxidation of methane

Anaerobic oxidation of methane(AOM) is an important biogeochemical process, which has important scientific significance for global climate change and atmospheric evolution. This research examined the δ~(34)S, terrigenous clastic indices of TiO_2 and Al_2O_3, and times for formation of the Ba front at site SH1, site SH3 and site 973-4 in the South China Sea. Three different coupling mechanisms of deposition rate and methane flux were discovered. The different coupling mechanisms had different effects on the role of AOM. At site 973-4, a high deposition rate caused a rapid vertical downward migration of the sulphate–methane transition zone(SMTZ), and the higher input resulted in mineral dissolution. At site SH3, the deposition rate and methane flux were basically in balance,so the SMTZ and paleo-SMTZ were the most stable of any site, and these were in a slow process of migration. At site SH1, the methane flux dominated the coupled mode, so the movement of the SMTZ at site SH1 was consistent with the general understanding. Understanding the factors influencing the SMTZ is important for understanding the early diagenesis process.     

九龙江河口沉积物中硫酸盐还原与甲烷厌氧氧化:同位素地球化学证据

通过沉积物柱孔隙水中甲烷,SO2-4,Cl-,δc(34S-SO2-4)、δc(13 C-CH4)的垂直分布特征,研究了硫酸盐还原和甲烷厌氧氧化(anaerobic oxidation of methane,简称AOM)过程在九龙江河口沉积物中的分布规律.测定结果显示两个站位(J-A和J-E)间隙水中SO2-4浓度随深...     

Using sediment geochemistry to infer temporal variation of methane flux at a cold seep in the South China Sea

Release of methane from the seafloor throughout the world's oceans and the biogeochemical processes involved may have significant effects on the marine sedimentary environment. Identification of such methane release events in marine sediment records can hence provide a window into the magnitude of ancient seeps. Here, we report on analysis of the geochemical composition of samples in a 12.3 m long sediment core (DH-5) collected from a seep site in the South China Sea (SCS). Our aim has been to investigate whether the evidence for the presence of methane release event within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary total sulfur (TS), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS) along with total organic carbon (TOC) and total inorganic carbon (TIC) content can be used to infer the presence of methane release events in cold seep settings. At least three methane release events were identified in the studied core (Unit I at 400–550 cm, Unit II at 740–820 cm, and Unit III at 1000–1150 cm). According to the characteristic of redox-sensitive elements (eg., Mo, U and Mn), we suggest that methane flux has been changed from relatively high (Unit I) to low (Unit II and III) rates. This inference is supported by the coupled occurrence of ³⁴S-enriched sulfides in Unit II and III. AMS ¹⁴C dates from planktonic foraminifera in Unit I suggest that high methane flux event occurred at ∼15.4–24.8 kyr BP, which probably resulted in locally-focused aerobic methane oxidation. Overall, our results suggest that TS, TOC, TIC and δ³⁴S_CRS have potential for identifying present and fossil methane release events in marine sediments.     

南海东沙东北部甲烷缺氧氧化作用的生物标志化合物及其碳同位素组成

南海东沙东北部碳酸盐岩和泥质沉积物中的生物标志化合物组合及其碳同位素组成分析表明,研究区内甲烷缺氧氧化作用(anaerobic oxidation of methane-AOM)发育.研究区内碳酸盐岩中含丰富的AOM标志化合物,2,6,11,15-四甲基十六烷(Crocetane-Cr.)、2,6,10,15,19-五甲基番茄烷(Pentamethylicosane-PMI)和2,6,10,15,19,23-六甲基二十四烷(Squalane-Sq角鲨烷)的13C亏损强烈(δ13C值介于-74.2‰~-119.0‰PDB之间),表明碳酸盐岩形成于AOM,同时反映该研究区曾发生过强烈、持续的富CH₄流体释放活动.柱状泥质沉积物中,AOM生物标志化合物在硫酸岩-甲烷过渡带(SMI-Sulfate-Methane Interface)边界附近相对丰度高,SMI之上样品中含量低,或未检出,表明现代环境在SMI附近有大量嗜甲烷微生物生长,使得深部上升的甲烷被大量消耗,很少有甲烷逸出海底.AOM生物标志化合物可用来指示SMI边界.不同站位、不同岩性AOM生物标志化合物组成(包括碳同位素组成)的差异反映了嗜甲烷古细菌组成的不同.     

Numerical modeling study of mineralization induced by methane cold seep at the sea bottom

In order to investigate the response of authigenic minerals to gas hydrate geo-systems, the biogeochemical processes and its induced mineralization were predicted by employing the comprehensive reactive transport modeling approach. Based on the available data extracted from the northern continental slope area of the South China Sea, a 1-D vertical column model was developed. Three cases with different upward methane flux rates and three cases with different mineral compositions, i.e., a total of six cases were designed to investigate the effects of variations in the depth of sulfate methane transition zone (SMTZ) and in the mineral composition on the formation of authigenic minerals. The simulation results indicate that the SMTZ depth influenced by both the upward methane flux rate and the initial composition played an important role in the formation of authigenic minerals. The AOM reaction is intensive at the interface, and the precipitation amount of calcite is large, which is mainly controlled by AOM. When the methane leakage rate is 20 times higher than the base case, aragonite starts to precipitate. During the simulation, oligoclase, k-feldspar, smectite-Na, smectite-Ca, chlorite dissolved. Our study specific to this area as a starting point may provide a quantitative approach for investigating carbonate and pyrite formation in hydrate-bearing sediments accounting for methane oxidation and sulfate reduction. The method presented here and the model built in this study can be used for other sites with similar conditions. In addition, this study may serve as an indication for the potential natural gas hydrate reservoir in depth, and is also significant for marine carbon and sulfur cycle.     

南海南部浅表层柱状沉积物孔隙水地球化学特征对甲烷渗漏活动的指示

海底沉积物孔隙水地球化学特征能快速响应甲烷渗漏活动及其生物地球化学过程,从而记录甲烷渗漏活动特征。对采自南海南部北康盆地的3个重力沉积柱状沉积物孔隙水样品（BH-H75、BH-H13Y和BH-H61）进行了甲烷浓度、溶解无机碳（DIC）和碳同位素（δ13CDIC）、阴离子（SO42−、Cl−）以及主微量元素（Ca2+、Mg2+、Sr2+、Ba2+）等地球化学分析。（△DIC+△Ca2++△Mg2+）/△SO42−比率图解与δ13CDIC深度剖面特征揭示了有机质硫酸盐还原反应（OSR）和硫酸盐驱动-甲烷厌氧氧化反应（SD-AOM）在不同沉积柱中所占比例的不同,其中BH-H13Y沉积柱中OSR和SD-AOM共同存在;BH-H75沉积柱中OSR占主导;在BH-H61沉积柱中SD-AOM占主导,且其底部可能存在微生物产甲烷作用。硫酸盐浓度线性拟合关系指示BH-H13Y的硫酸盐-甲烷过渡带（SMTZ）的深度约为700 cmbsf。结合SO42−浓度、DIC浓度最大值和δ13CDIC最小值推测BH-H61的SMTZ深度约为480 cmbsf。BH-H61和BH-H13Y沉积柱中,较浅的SMTZ深度、上升的DIC浓度以及强烈负偏的δ13CDIC值指示研究区存在甲烷渗漏活动。此外,在BH-H61和BH-H13Y站位,硫酸盐浓度随深度降低的变化梯度在沉积柱下部较上部陡,指示向上迁移的甲烷通量在时间上逐渐增强。孔隙水中Ca2+、Mg2+、Sr2+浓度以及Mg/Ca、Sr/Ca比值变化特征指示研究区沉积物中可能有自生高镁方解石矿物生成;而BH-H61站位SMTZ界面以下,孔隙水中Ba2+浓度升高,指示了硫酸钡的溶解作用。     

南海东北部冷泉区沉积物中有机质来源的生物标志物分析与环境指示意义

Multi-biomarker indexes were analyzed for two piston cores from potential cold seep areas of the South China Sea off southwestern Taiwan. Total organic carbon(TOC) normalized terrestrial(n-alkanes) and marine(brassicasterol, dinosterol, alkenones and iso-GDGTs) biomarker contents and ratios(TMBR, 1/Pmar-aq, BIT) were used to evaluate the contributions of terrestrial and marine organic matter(TOM and MOM respectively) to the sedimentary organic matter, indicating that MOM dominated the organic sources in Core MD052911 and the sedimentary organic matter in Core ORI-_(86)0-22 was mainly derived from terrestrial inputs, and different morphologies were the likely reason for TOM percentage differences. BIT results suggested that river-transported terrestrial soil organic matter was not a major source of TOM of sedimentary organic matter around these settings.Diagnostic biomarkers for methane-oxidizing archaea(MOA) were only detected in one sample at 172 cm depth of Core ORI-_(86)0-22, with abnormally high iso-GDGTs content and Methane Index(MI) value(0.94). These results indicated high anaerobic oxidation of methane(AOM) activities at or around 172 cm in Core ORI-_(86)0-22.However in Core MD052911, MOA biomarkers were not detected and MI values were lower(0.19–0.38), indicated insignificant contributions of iso-GDGTs from methanotrophic archaea and the absence of significant AOM activities. Biomarker results thus indicated that the discontinuous upward methane seepage and insufficient methane flux could not induce high AOM activities in our sampling sites. In addition, the different patterns of TEX_(86) and U_(37)~(K′) temperature in two cores suggested that AOM activities affected TEX_(86)37 temperature estimates with lower values in Core ORI-_(86)0-22, but not significantly on TEX_(86) temperature estimates in Core MD052911.     

南海北部琼东南盆地浅表层沉积物的地球化学特征及对沉积环境的指示*

南海北部琼东南盆地海底存在着巨型麻坑, 现有研究多认为其形成主要与海底流体渗漏有关。目前对琼东南盆地深海沉积物地球化学特征及麻坑区的生物地球化学过程等尚不清楚。文章选取南海北部琼东南盆地C14、C19两个站位岩心样品, 进行了总硫(TS)、总碳(TC)、总有机碳(TOC)、铬还原性硫化物(CRS)及其δ³⁴S_CRS值测试, 并结合总氮/总碳(TN/TOC)比值和已发表的孔隙水中SO₄^2-浓度等进行了地球化学特征分析。研究表明: C14站位以3.91m bsf (below seafloor)为界, 上下分别存在有机质参与的硫酸盐还原反应(OSR)和甲烷厌氧氧化作用(AOM)驱动的硫酸盐还原反应(SR); 3.91m bsf以上的部位沉积物的TS、TC含量均低于3.91m bsf以下部位, 且沉积物孔隙水中SO₄^2-浓度由3.91m bsf以上的缓慢凹型减少变成3.91m bsf以下的线性减少, 说明该处成为沉积物中地球化学特征分界的明显标志; 在3.91m bsf以下, 受到甲烷渗漏的影响。C19站位沉积物中TS与TC含量由浅到深逐渐增加, 但与TN/TOC比值变化呈现几乎相反趋势, 即整个岩心以OSR为主, 并呈现出有机质早期成岩阶段的沉积现象。C14和C19两个站位柱状沉积物的δ³⁴S_CRS值变化范围分别为-50.2‰~-46.9‰和-50.1‰~-42.0‰ (V-CDT标准), 均显示出了较为偏负的硫同位素值, 表明研究区主要的生物化学过程是在相对开放体系下硫酸盐还原作用的结果, 综合说明该研究区麻坑的甲烷流体已经喷发, 目前可能处于衰退期, 甚至已经不活跃, 该结果与前人的认识基本一致。     

南海北部琼东南盆地冷泉区表层沉积物微量元素的分析及其对甲烷渗漏的指示

Recent studies have shown that specific geochemical characteristics of sediments can be used to reconstruct past methane seepage events. In this work, the correlation between the Sr/Ca and Mg/Ca ratios of sediment samples is analyzed and the sulfate concentration profile in Site C14 from cold-seep sediments in the Qiongdongnan Basin in northern South China Sea is obtained. The results confirmed that, sulfate at 0–247 cm below sea floor(Unit I) is mainly consumed by organic matter sulfate reduction(OSR), while sulfate at 247–655 cm(Unit II) is consumed by both the OSR and the anaerobic oxidation of methane(AOM). In addition, the bottom sediment layer is affected by weak methane seepage. The Mo and U enrichment factors also exhibit similar trends in their respective depth profiles. The responses of trace elements, including Co/Al, Ni/Al, Cr/Al and Zn/Al ratios to methane seepage allowed the study of depositional conditions and methane seepage events. Based on the results, it is speculated that the depositional conditions of Unit II changed with depth from moderate conditions of sulfidic and oxic conditions to locally anoxic conditions, and finally to suboxic conditions due to methane fluid leakage. The stable isotope values of chromium-reducible sulfide produced by AOM and those of sulfide formed by OSR in the early diagenetic environment suffered serious depletion of 34 S. This was probably due to weak methane leakage, which caused the slower upward diffusion and the effect of early diagenesis on the samples. It is necessary to consider the effects of depositional environments and diagenesis on these geochemical parameters.